An easy way to improve league importance and chat rooms in general.
What if Riot made the chat rooms for each of leagues.(I.E Karthus's Highway men, or Cassioepa's rogues.) Chat rooms would be available only to the users in their respective leagues and would not be required to be in it. It would give a chance to make the league system more important and give solo queue players a better way to find duo partners.
You could probably add a function where it appears when you click the chat icon, it would show the league you are in such as Silver,Nasus's Spellslingers and have a chat where anyone in that specific league would be able to enter. You could also increase accessibility by inputting a button to enter the chat when you look at the profile.
Tl;Dr Chat rooms need to be improved in general and to personalize and give a meaning toward the league system.